Extending differential optical absorption spectroscopy for limb measurements in the UV

Methods of UV/VIS absorption spectroscopy to determine the constituents in the Earth's atmosphere from measurements of scattered light are often based on the Beer-Lambert law, like e.g. Differential Optical Absorption Spectroscopy (DOAS). While the Beer-Lambert law is strictly valid for a single light path only, the relation between the optical depth and the concentration of any absorber can be approximated as linear also for scattered light observations at a single wavelength if the absorption is weak. If the light path distribution is approximated not to vary with wavelength, also linearity between the optical depth and the product of the cross-section and the concentration of an absorber can be assumed. These assumptions are widely made for DOAS applications for scattered light observations. <br><br> For medium and strong absorption of scattered light (e.g. along very long light-paths like in limb geometry) the relation between the optical depth and the concentration of an absorber is no longer linear. In addition, for broad wavelength intervals the differences in the travelled light-paths at different wavelengths become important, especially in the UV, where the probability for scattering increases strongly with decreasing wavelength. <br><br> However, the DOAS method can be extended to cases with medium to strong absorptions and for broader wavelength intervals by the so called air mass factor modified (or extended) DOAS and the weighting function modified DOAS. These approaches take into account the wavelength dependency of the slant column densities (SCDs), but also require a priori knowledge for the air mass factor or the weighting function from radiative transfer modelling. <br><br> We describe an approach that considers the fitting results obtained from DOAS, the SCDs, as a function of wavelength and vertical optical depth and expands this function into a Taylor series of both quantities. The Taylor coefficients are then applied as additional fitting parameters in the DOAS analysis. Thus the variability of the SCD in the fit window is determined by the retrieval itself. <br><br> This new approach provides a description of the SCD the exactness of which depends on the order of the Taylor expansion, and is independent from any assumptions or a priori knowledge of the considered absorbers. <br><br> In case studies of simulated and measured spectra in the UV range (332–357 nm), we demonstrate the improvement by this approach for the retrieval of vertical profiles of BrO from the SCIAMACHY limb observations. The results for BrO obtained from the simulated spectra are closer to the true profiles, when applying the new method for the SCDs of ozone, than when the standard DOAS approach is used. For the measured spectra the agreement with validation measurements is also improved significantly, especially for cases with strong ozone absorption. <br><br> While the focus of this article is on the improvement of the BrO profile retrieval from the SCIAMACHY limb measurements, the novel approach may be applied to a wide range of DOAS retrievals

Accounting for the effect of horizontal gradients in limb measurements of scattered sunlight

Limb measurements provided by the SCanning Imaging Absorption spectrometer for Atmospheric CHartographY (SCIAMACHY) on the ENVISAT satellite allow retrieving stratospheric profiles of various trace gases on a global scale, among them BrO for the first time. For limb observations in the UV/VIS spectral region the instrument measures scattered light with a complex distribution of light paths: the light is measured at different tangent heights and can be scattered or absorbed in the atmosphere or reflected by the ground. By means of spectroscopy and radiative transfer modelling these measurements can be inverted to retrieve the vertical distribution of stratospheric trace gases. <br></br> The fully spherical 3-D Monte Carlo radiative transfer model "Tracy-II" is applied in this study. The Monte Carlo method benefits from conceptual simplicity and allows realizing the concept of full spherical geometry of the atmosphere and also its 3-D properties, which is important for a realistic description of the limb geometry. Furthermore it allows accounting for horizontal gradients in the distribution of trace gases. <br></br> In this study the effect of horizontally inhomogeneous distributions of trace gases along flight/viewing direction on the retrieval of profiles is investigated. We introduce a tomographic method to correct for this effect by combining consecutive limb scanning sequences and utilizing the overlap in their measurement sensitivity regions. It is found that if horizontal inhomogenity is not properly accounted for, typical errors of 20% for NO<sub>2</sub> and up to 50% for OClO around the altitude of the profile peak can arise for measurements close to the Arctic polar vortex boundary in boreal winter

Is a scaling factor required to obtain closure between measured and modelled atmospheric O₄ absorptions? An assessment of uncertainties of measurements and radiative transfer simulations for 2 selected days during the MAD-CAT campaign

In this study the consistency between MAX-DOAS measurements and radiative transfer simulations of the atmospheric O4 absorption is investigated on 2 mainly cloud-free days during the MAD-CAT campaign in Mainz, Germany, in summer 2013. In recent years several studies indicated that measurements and radiative transfer simulations of the atmospheric O4 absorption can only be brought into agreement if a so-called scaling factor (<1) is applied to the measured O4 absorption. However, many studies, including those based on direct sunlight measurements, came to the opposite conclusion, that there is no need for a scaling factor. Up to now, there is no broad consensus for an explanation of the observed discrepancies between measurements and simulations. Previous studies inferred the need for a scaling factor from the comparison of the aerosol optical depths derived from MAX-DOAS O4 measurements with that derived from coincident sun photometer measurements. In this study a different approach is chosen: the measured O4 absorption at 360 nm is directly compared to the O4 absorption obtained from radiative transfer simulations. The atmospheric conditions used as input for the radiative transfer simulations were taken from independent data sets, in particular from sun photometer and ceilometer measurements at the measurement site. This study has three main goals: first all relevant error sources of the spectral analysis, the radiative transfer simulations and the extraction of the input parameters used for the radiative transfer simulations are quantified. One important result obtained from the analysis of synthetic spectra is that the O4 absorptions derived from the spectral analysis agree within 1 % with the corresponding radiative transfer simulations at 360 nm. Based on the results from sensitivity studies, recommendations for optimised settings for the spectral analysis and radiative transfer simulations are given. Second, the measured and simulated results are compared for 2 selected cloud-free days with similar aerosol optical depths but very different aerosol properties. On 18 June, measurements and simulations agree within their (rather large) uncertainties (the ratio of simulated and measured O4 absorptions is found to be 1.01±0.16). In contrast, on 8 July measurements and simulations significantly disagree: for the middle period of that day the ratio of simulated and measured O4 absorptions is found to be 0.82±0.10, which differs significantly from unity. Thus, for that day a scaling factor is needed to bring measurements and simulations into agreement. Third, recommendations for further intercomparison exercises are derived. One important recommendation for future studies is that aerosol profile data should be measured at the same wavelengths as the MAX-DOAS measurements. Also, the altitude range without profile information close to the ground should be minimised and detailed information on the aerosol optical and/or microphysical properties should be collected and used. The results for both days are inconsistent, and no explanation for a O4 scaling factor could be derived in this study. Thus, similar but more extended future studies should be performed, including more measurement days and more instruments. Also, additional wavelengths should be included

Quantification and parametrization of non-linearity effects by higher-order sensitivity terms in scattered light differential optical absorption spectroscopy

We address the application of differential optical absorption spectroscopy (DOAS) of scattered light observations in the presence of strong absorbers (in particular ozone), for which the absorption optical depth is a non-linear function of the trace gas concentration. This is the case because Beer–Lambert law generally does not hold for scattered light measurements due to many light paths contributing to the measurement. While in many cases linear approximation can be made, for scenarios with strong absorptions non-linear effects cannot always be neglected. This is especially the case for observation geometries, for which the light contributing to the measurement is crossing the atmosphere under spatially well-separated paths differing strongly in length and location, like in limb geometry. In these cases, often full retrieval algorithms are applied to address the non-linearities, requiring iterative forward modelling of absorption spectra involving time-consuming wavelength-by-wavelength radiative transfer modelling. In this study, we propose to describe the non-linear effects by additional sensitivity parameters that can be used e.g. to build up a lookup table. Together with widely used box air mass factors (effective light paths) describing the linear response to the increase in the trace gas amount, the higher-order sensitivity parameters eliminate the need for repeating the radiative transfer modelling when modifying the absorption scenario even in the presence of a strong absorption background. While the higher-order absorption structures can be described as separate fit parameters in the spectral analysis (so-called DOAS fit), in practice their quantitative evaluation requires good measurement quality (typically better than that available from current measurements). Therefore, we introduce an iterative retrieval algorithm correcting for the higher-order absorption structures not yet considered in the DOAS fit as well as the absorption dependence on temperature and scattering processes

The effect of horizontal gradients and spatial measurement resolution on the retrieval of global vertical NO2 distributions from SCIAMACHY measurements in limb only mode

Limb measurements provided by the Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) on the ENVISAT satellite allow retrieving stratospheric profiles of various trace gases on a global scale. Combining measurements of the same air volume from different viewing positions along the orbit, a tomographic approach can be applied and 2-D distribution fields of stratospheric trace gases can be acquired in one inversion. With this approach, it is possible to improve the accounting for the effect of horizontal gradients in the trace gas distribution on the profile retrieval. This was shown in a previous study for the retrieval of NO2 and OClO profiles in the Arctic region near the polar vortex boundary. In this study, the tomographic retrieval is applied on measurements during special limb-only orbits performed on 14 December 2008. For these orbits the distance between consecutive limb scanning sequences was reduced to ~3.3° of the orbital circle (i.e. more than two times with respect to the nominal operational mode). Thus, the same air volumes are scanned successively by more than one scanning sequence also for midlatitudes and the tropics. It is found that the profiles obtained by the tomographic 2-D approach show significant differences to those obtained by the 1-D approach. In particular, for regions close to stratospheric transport barriers (i.e. near to the edge of the polar vortex and subtropical transport barrier) up to 50% larger or smaller NO2 number densities (depending on the sign of the gradient along the line of sight) for altitudes below the peak of the profile (around 20 km) are obtained. The limb-only measurements allow examining the systematic error if the horizontal gradient is not accounted for, and studying the impact of the gradient strength on the profile retrieval on a global scale. The findings for the actual SCIAMACHY observations are verified by sensitivity studies for simulated data for which the NO2 distributions to be retrieved are known in advance. In addition, the impact of the horizontal distance between consecutive limb scanning sequences on the quality of the tomographic 2-D retrieval is investigated and a possibility to take into account the horizontal gradients by an interpolation approach is studied

Retrieval of tropospheric column densities of NO₂ from combined SCIAMACHY nadir/limb measurements

The SCIAMACHY instrument onboard the ESA satellite ENVISAT allows measurements of various atmospheric trace gases, such as NO2. A unique feature of SCIAMACHY is that measurements are made alternately in limb and nadir mode. The limb measurements provide an opportunity for directly determining stratospheric column densities (CDs), which are needed to extract tropospheric CDs from the total CD measurements performed in (quasi simultaneous) nadir geometry. Here we discuss the potential and limitations of SCIAMACHY limb measurements for estimating stratospheric CDs of NO2 in comparison to a simple reference sector method, and the consequences for the resulting tropospheric CDs. A direct, absolute limb correction scheme is presented that improves spatial patterns of tropospheric NO2 column densities at high latitudes, but results in artificial zonal stripes at low latitudes. Subsequently, a relative limb correction scheme is introduced that successfully reduces stratospheric artefacts in the tropospheric data product without introducing new ones. This relative limb correction scheme is rather simple, robust, and, in essence, based on measurements alone. The effects of the different stratospheric estimation schemes on tropospheric CDs are discussed with respect to zonal and temporal dependencies. In addition, we define error quantities from the nadir/limb measurements that indicate remaining systematic errors as a function of latitude and day. Our new suggested stratospheric estimation scheme, the relative limb correction, improves mean tropospheric slant CDs significantly, e.g. from &minus;1&times;1015 molec/cm2 (using a reference sector method) to &asymp;0 in the Atlantic ocean, and from +1&times;1015 molec/cm2 to &asymp;0 over Siberia, at 50&deg; N in January 2003–2008